CN105829385A

CN105829385A - Polyurethane foam and process for producing same

Info

Publication number: CN105829385A
Application number: CN201480060657.5A
Authority: CN
Inventors: S.林德纳; W.弗里德里希斯; M.尼斯滕; R.施特里; T.佐特曼; N.贝克; A.查尔比; D.恩格伦; P.海因茨
Original assignee: Bayer MaterialScience AG
Current assignee: Covestro Deutschland AG
Priority date: 2013-11-08
Filing date: 2014-11-07
Publication date: 2016-08-03
Anticipated expiration: 2034-11-07
Also published as: MX2016005916A; KR20160084845A; EP3066144B1; WO2015067751A1; CA2928632A1; TR201903415T4; US10131759B2; US20160264749A1; CN105829385B; JP2016537466A; EP3066144A1

Abstract

A polyurethane foam, polyisocyanurate foam or polyurea foam is obtainable from the reaction of a mixture comprising A) a compound reactive towards isocyanate ("NCO-reactive compound"); B) a blowing agent selected from the group comprising linear, branched or cyclic C1 to C6 hydrocarbons, linear,branched or cyclic C1 to C6 fluorocarbons, N2, O2, argon and/or CO2, where the blowing agent B) is present in the supercritical or near-critical state; C) a polyisocyanate; D) an amphiphilic isocyanate; and E) optionally a surfactant and F) optionally other auxiliaries and additives. The invention further relates to the production of this polyurethane foam, where the blowing agent is emulsified in the isocyanate component containing amphiphilic isocyanate.

Description

Polyurethane foam and preparation method thereof

The present invention relates to polyurethane foam, it can be obtained by the reaction of the mixture comprising following component: A) isocyanates is anti- Answering property compound；B) foaming agent, it is selected from linear, branched or ring-type C₁-C₆Hydrocarbon, linear, branched or ring-type C₁-C₆Fluorine-containing Hydrocarbon, N₂、O₂, argon and/or CO₂, wherein said foaming agent B) and it is in supercritical or near critical state；C) polyisocyanates, D) two Parent's property isocyanates and optional E) surfactant and optional F) other auxiliary agent and additive.

The invention further relates to prepare the method for this type of polyurethane foam.

In the present context, title " polyurethane foam " also includes polyureas and polyisocyanurate foam.

The polymer foams of nano-cellular or nanoporous considers it is the best adiabator based on theory.This The inside dimension being because this foaming structure is positioned at the scope of gas molecule mean free path length.So can reduce and be used for The content of the gas of heat transfer.Polyurethane is a base polymer conventional in thermal insulation.

Polyurethane foam is prepared by the reaction of polyol component (the most also can contain foaming agent) with isocyanates.Isocyanide Acid esters forms carbon dioxide with the reaction of water, and carbon dioxide also acts as foaming agent.

For formation of foam and therefore for later solidification foam abscess-size for decisive step be foaming The nucleation of agent, because each abscess in foam is produced by bubble.This be can be observed, bubble the newest after nucleation Produce, but foaming agent diffuses in the bubble existed.

Add stabilizer and facilitate the emulsifying of different component, affect nucleation and prevent the bubble coalescence grown up.They also shadows Ring abscess to open.In open celled foam, the film in the hole of growth is open, leaves the supporter (Steg) in hole.

One possible method is by the emulsifying then in decompression in described reactant mixture of postcritical foaming agent After make this foam curing.Known POSME method (supercritical microemulsion dilating principle) is its variant.Wherein, foaming agent is with microemulsion Presented in.Microemulsion is formed under particularly depending on the specified conditions of emulsifier concentration and temperature.The feature of microemulsion exists In, it has stability and nonpolar phase, and foaming agent the most in the case can be present in pole with the least droplet form Property mutually in.The diameter of this type of microdroplet can be 1-100 nm.

DE 102 60 815 A1 discloses material and the preparation method of described expanded material of foaming.It is said that tool can be produced There is the expanded material of nanometer foam bubble, without overcoming the energy barrier often occurred in phase in version and nucleation process.With This relevant target is controllably to produce to have 10¹²To 10¹⁸/cm³Foam bubbles number density and the foam of 10 nm to 10 m The expanded material of bubble mean diameter.Basis is to make second fluid be dispersed in the substrate of first fluid with the form of pond (Pool) In.Reaction compartment exists the first fluid as substrate and the second fluid of pond form.By changing pressure and/or temperature, Second fluid is made to be changed near critical or the supercriticality with the density close to liquid.Second fluid is the most completely or nearly Existing with pond form completely, it is evenly distributed in whole first fluid.Decompression makes second fluid return to gaseous density shape State, thus pond expands and forms nanometer foam bubble.Energy barrier need not be overcome, and Blowing agent molecules need not diffuse to growth Bubble.

Here, generally advise that polymerisable material is used as first fluid.But, only specifically mention polymerization and form polyacrylamide The acrylamide of amine and polymerization form the tripolycyanamide of melmac.Second fluid should be selected from comprising the substance classes of hydrocarbon such as Methane or ethane, and alkanol, fluorochlorohydrocarbon or CO₂.In addition the block and extremely should with at least one affine first fluid is used The amphipathic nature material of the block of a few affine second fluid.

WO 2012/146568 discloses a kind of polyurethane foam, and it can be obtained by the reaction of the mixture comprising following component : A) isocyanate-reactive compound；B) foaming agent, it is selected from linear, branched or ring-type C₁-C₆Hydrocarbon, linear, branched or Ring-type C1-C6 hydrofluorocarbons, N₂、O₂, argon and/or CO₂, wherein said foaming agent B) and it is in supercritical or near critical state；With C) polyisocyanates.

Described isocyanate-reactive compound A) comprise hydrophobic parts and have hydrophilic parts and more than 1 average Hydroxy functionality.Described hydrophobic parts comprises and has the saturated of at least 6 carbon atoms or undersaturated hydrocarbon chain, and described hydrophilic Property part comprises oxyalkylene units and/or ester units.

It is an object of the invention to provide the polyurethane foam of nano-cellular, it can be by described in WO 2012/146568 Prepared by the alternative method of method, but wherein foaming agent is also in stabilisation in microemulsion.

According to the present invention, this purpose is real by being come by the available polyurethane foam of reaction of the mixture comprising following component Existing:

A) isocyanate-reactive compound (" NCO reactive compounds ")；

B) foaming agent, it is selected from linear, branched or ring-type C₁-C₆Hydrocarbon, linear, branched or ring-type C₁-C₆Hydrofluorocarbons, N₂、 O₂, argon and/or CO₂, wherein said foaming agent C) and it is in supercritical or near critical state；

C) polyisocyanates；

D) amphipathic isocyanates；With

E) optional surfactant；With

F) other optional auxiliary agent and additive.

It is surprisingly found that, by using amphipathic isocyanates D) foaming agent, particularly CO can also be prepared₂ Microemulsion, this microemulsion can be further processed into polyurethane foam.Therefore, described foaming agent is finely dispersed in the phase of oneself In, thus can prepare the foam of special pore.When using the blowing agent blends of supercritical or near critical state, it is not necessary to Nucleating step.Therefore the foam of pore can be prepared.

Component D), amphipathic isocyanates, is by polarity (hydrophilic) part and nonpolar (hydrophobicity/lipotropy) part The compound constituted.Component D) can on the one hand be considered as thus surfactant, it is considered as on the other hand polyurethane Reactant in Bei.

Surfactant can use HLB value (hydrophil lipophil balance) to characterize, and it passes through hydrophilic parts and lipophilic moieties Mass ratio measure.The HLB value of nonionic surfactant can be calculated as below: HLB=20 x (1 Mh/M), wherein Mh is The molal weight of the hydrophobic parts of molecule, M is the molal weight of whole molecule.The HLB value of amphipathic isocyanates can be with example As for 1-18, preferably 2-17, particularly preferred 3-16.

Amphipathic isocyanates D) can by polyisocyanates with Ze Lieweijinuofu active hydrogen atom (such as OH, NH) and thus prepared by the polarity of isocyanate-reactive or the reaction of non-polar compound.Below will be from this kind The compound of class is separately or cooperatively referred to as " OH component ".

Depend on that polyisocyanates and the selection of OH component, described OH component can be hydrophobic in amphipathic isocyanates Property (lipotropy) or hydrophilic parts.

In amphipathic isocyanates, which kind of molecular moiety is " hydrophilic " or " lipophobia ", and this is not by corresponding molecule The absolute polarity value of part determines, but which kind of molecular moiety to have bigger affinity for the material of bigger polarity by Determine.The amphipathic relative polarity difference from there through molecular moiety determines.

Such as, the OH component selected from one or more following compounds is being used: comprise and there is the full of at least 4 carbon atoms With or the unitary of undersaturated hydrocarbon chain and when polyhydric alcohol, fatty alcohol, amine and amino alcohol, the OH component in amphipathic isocyanates Form hydrophobic parts and polyisocyanates forms hydrophilic parts.

Such as, when using the simple function of oxirane with high-load or multifunctional polyoxyalkylene as OH component, It forms hydrophilic parts in amphipathic isocyanates and polyisocyanates forms hydrophobic parts.

Amphipathic isocyanates D) generally by the NCO base of the isocyanate-reactive group of OH component with polyisocyanates Prepared by the reaction of group.Here, such as polyisocyanates and OH component are mutually bonded via carbamate groups or urea groups. In reactant mixture, the isocyanate groups of excess guarantees to obtain the also amido-containing acid ester-and/or the two of urea groups of NCO official's energy Parent's property isocyanates.

It is that there is >=the isocyanide of the average NCO functionality of 2 for preparing the polyisocyanates of described amphipathic isocyanates Acid esters.

The example of this type of suitable polyisocyanates includes 1,4-fourth diisocyanate, 1,5-penta diisocyanate, 1,6- Hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4-and/or 2,4,4-trimethyl six are sub- Double (4,4'-isocyanatocyclohexyl) methane of methyl diisocyanate, isomery or its there is the mixing of any content of isomer Thing, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-and/or 2,6-toluene di-isocyanate(TDI) (TDI), 1,5- Naphthalene diisocyanate, 2,2'-and/or 2,4'-and/or 4,4'-methyl diphenylene diisocyanate (MDI) and/or higher level are same It is thing (polymeric MDI), double (2-isocyanato--propyl-2-yl)-benzene (TMXDI) of 1,3-and/or l, 4-, the double (isocyano of l, 3- Close methyl) benzene (XDI) and containing 2,6-bis-isocyanato-caproic acid Arrcostab (lysine two Carbimide. of C1 to C6 alkyl Ester).Wherein it is preferred from the isocyanates of methyl diphenylene diisocyanate series.

In addition to above-mentioned polyisocyanates, it is also possible to use certain content has urea diketone, isocyanuric acid ester, carbamic acid Ester, carbodiimide, uretonimine, allophanate, biuret, amide, imido are tied for oxadiazinediones and/or diazine triketone The modifying diisocyanates of structure and per molecule contain the unmodified polyisocyanates such as 4-Carbimide. of more than two NCO group Root closes methyl isophthalic acid, 8-octane diisocyanate (nonane triisocyanate) or tritan .-4,4', 4 "-triisocyanates.

The compound that can be used as OH component has hydroxyl and/or Ammonia official's energy.

The example of this compounds includes having and comprises the unitary of the saturated of at least 4 carbon atoms or aliphatic unsaturated hydrocarbon or many Unit's alcohol or isocompound such as butanol, hexanol, capryl alcohol, decanol, tridecyl alcohol and the hexadecanol of fatty alcohol, such as alkanol, with And 2-ethyl-1-hexanol, 12-hydroxystearyl alcohol, oleyl alcohol, erucyl alcohol, sub-oleyl alcohol, linolenyl alcohol, arachidic alcohol, gaducene alcohol, wooden dipper Dish alcohol and two lanolin alcohols.

Preferably butanol, particularly n-butyl alcohol, hexanol, capryl alcohol, particularly 2-ethyl-1-hexanol, decanol, hexadecanol, 12- Hydroxystearyl alcohol and oleyl alcohol.

The example of polyhydric alcohol includes the isocompound of alkanediol, such as butanediol, pentanediol, hexanediol, heptandiol, Ethohexadiol and there is higher molecular weight α of 9-18 carbon atom, ω-alkanediol, particularly 2-methyl isophthalic acid, ammediol, 2, 2-dimethyl-1,3-propylene glycol, 2-butyl-2-ethyl-1,3-propanediol and polyhydric alcohol such as 1,2,6-hexanetriol, 1,1,1-tri- Hydroxymethyl-propane, 2,2-(double (methylol)-1,3-propylene glycol, 1,2,4-butantriol, 1,2,6-hexanetriol, double (trihydroxy methyl third Alkane), tetramethylolmethane, mannitol, methylglycoside, dimer diols (hydrogenated products of=dimer fatty acid methyl ester) and Oleum Ricini. Preferably butanediol, pentanediol, hexanediol, heptandiol and ethohexadiol, particularly 2-methyl isophthalic acid, ammediol, 2,2-dimethyl-1, Ammediol and 2-butyl-2-ethyl-1,3-propanediol and 1,2,6-hexanetriol, 1,1,1-trimethylolpropane, 2,2-are (double (methylol)-1,3-propylene glycol, 1,2,4-butantriol, 1,2,6-hexanetriol, dimer diols and Oleum Ricini.

Other preferred alcohol is simple function or polyfunctional polyoxyalkylene, and the OH value that it has is 10-600, preferably 20- 112, it can have the ethylene oxide content of 50-100 mole of %, preferably 60-100 mole of %, based on contained oxyalkylene group, The most such as total amount meter of methoxyl group (polyethylene glycol oxide).

The amine being applicable to amphipathic isocyanates is to have the simple function of at least 4 carbon atoms or polyfunctional amine.Example Including primary monoamines, such as 1-butylamine, 1-hexylamine, 2-ethylhexylamine, 1-octylame, 1-decyl amine, 1-lauryl amine, 1-18-amine.；Amino Ethylpyridine and polyetheramine are (such as from the Jeffamine M series of Huntsman Corp., such as Jeffamine M- 600 or Jeffamine M-1000, and/or comprise uncle and/or diamidogen (such as 1,4-Diaminobutane, l, the 2-of secondary amino group Double (methylamino) ethane, DAMP, 1,6-diamino hexane, 1,8-diamino-octane, 1,9-diamino nonane, 1,10-diamino decane, 1,12-diamino dodecane, polyether diamine such as Jeffamine D series polyether diamidogen, such as Jeffamine® D-230、Jeffamine® D-400、Jeffamine® D-2000、Jeffamine® D-4000；Bag Containing uncle and/or the aliphatic triamine of secondary amino group, such as triaminononane (4-amino methyl-l, 8-octamethylenediamine)；Polyetheramine, such as Jeffamine T series polyether amine, such as Jeffamine T-403, Jeffamine T-3000, Jeffamine T-5000)。

Amphipathic isocyanates can also use amino alcohol to prepare.Preferably amino-n-butyl alcohol；4-amino-n-butyl alcohol is with double (2-hydroxypropyl) amine.

The mixture of compounds mentioned above and classes of compounds can also be used as OH component.

Described amphipathic isocyanates is comprising A)-F) whole reactant mixture in content can be 5-70 weight %, Preferably 7-60 weight % and particularly preferred 8.5-50 weight %.

Isocyanate groups in polyisocyanate component is compared to the isocyanate-reactive group in OH component It is 1:0.001-1:0.8 for preparing amphipathic isocyanates, preferably 1:0.05-1:0.6 and particularly preferably 1:0.08-1: 0.5。

The reaction of polyisocyanates and the OH component amphipathic isocyanates of offer can at urethanation catalyst such as Carry out in the presence of tin compound, zinc compound, amine, guanidine or amidine or in the presence of allophanatization catalyst is such as zinc compound. This reaction, generally at 25 DEG C-140 DEG C, is carried out at preferably 60 DEG C-100 DEG C.

Available NCO reactive compounds A) particularly including polyhydric alcohol, polyamines, polynary amino alcohol And multi-thiol (Polyaminoalkohol).

The example of polyamines includes that ethylenediamine, 1,2-and 1,3-diaminopropanes, 1,4-diaminobutane, 1,6-diaminourea are own Alkane, isophorone diamine, the isomer mixture of 2,2,4-and 2,4,4-trimethylhexamethylenediamine, 2-methyl pentamethylene Diamidogen, Diethylenetriamine, 1,3-and 1,4-benzene dimethylamine, α, α, α ', α '-tetramethyl-1,3-and-1,4-benzene dimethylamine and 4,4'- Diamino-dicyclohexyl methane, diethylmethyl phenylenediamine (DETDA), 4,4'-diaminourea-3,3'-dichloro-diphenyl methane (MOCA), dimethyl-ethylenediamine, 1,4-double (amino methyl) hexamethylene, 4,4'-diaminourea-3,3'-dimethyidicyclohexyl first Alkane and 4,4'-diaminourea-3,5-diethyl-3', 5'-diisopropyl dicyclohexyl methyl hydride.Also suitable is polymerized polyamines as poly- Oxidation enamine (Polyoxyalkylenamin).

The example of amino alcohol includes N-amino ethyl ethanolamine, ethanolamine, 3-aminopropanol, neopentyl alcohol amine and diethanol Amine.

The example of multi-thiol includes two (2-mercaptoethyl) ether, tetramethylolmethane four mercaptoacetate, tetramethylolmethane four (3- Mercaptopropionic acid ester) and double ((2-mercaptoethyl) the sulfenyl)-3-thio propane of 1,2-.

In a preferred embodiment of the reaction system of the present invention, compound A) there is the sense for isocyanates Degree is 1.8-6.0, particularly >=2.0.

Number-average molecular weight Mn for example, >=62 g/mol that described polyhydric alcohol can have to≤8000 g/mol, preferably >=90 g/mol to≤5000 g/mol and more preferably >=92 g/mol to≤1000 g/mol.Adding single polyol In the case of, component A) OH value represent described polyhydric alcohol OH value.In the case of mixture, represent average OH value.This value Can determine according to DIN 53240.The average OH functionality such as >=2, for example, >=2 to≤6 of described polyhydric alcohol, preferably >= 2.1 to≤4, and more preferably >=2.2 to≤3.

The polyether polyol that can use includes such as by available poly-four Asias of the cation ring-opening polymerization of oxolane Methyl glycol polyethers.

Equally suitable polyether polyol is styrene oxide, oxirane, expoxy propane, epoxy butane and/or table chlorine Alcohol addition compound product in two-or multifunctional starter molecules.

Suitably starter molecules be such as water, ethylene glycol, diethylene glycol, butyldiglycol, glycerol, diethylene glycol, three Hydroxymethyl-propane, propylene glycol, tetramethylolmethane, Sorbitol, sucrose, ethylenediamine, toluenediamine, triethanolamine, 1,4-butanediol, The low-molecular-weight ester of the hydroxyl of 1,6-HD and such polyhydric alcohol and dicarboxylic acids.

Suitably PEPA especially includes two-and three-and tetrol and two-and three-and tetrabasic carboxylic acid or hydroxyl carboxylic Acid or the condensation polymer of lactone.Replace described free polycarboxylic acid, it is also possible to use corresponding multi-carboxy anhydride or corresponding lower alcohol many Described polyester prepared by carboxylate.

The suitably example of glycol includes the most poly-second of ethylene glycol, butanediol, diethylene glycol, triethylene glycol, ployalkylene glycol Glycol, and 1,2-PD, 1,3-PD, butanediol (1,3), butanediol (Isosorbide-5-Nitrae), hexanediol (1,6) and isomer, new Pentanediol or 3-hydroxypivalic acid DOPCP.Further, it is also possible to use polyhydric alcohol such as trimethylolpropane, glycerol, erithritol, Tetramethylolmethane, trihydroxy methyl benzene or tris(2-hydroxy ethyl)isocyanurate.

Available polycarboxylic acid include such as phthalic acid, M-phthalic acid, p-phthalic acid, tetrahydrophthalic acid, Hexahydrophthalic acid, cyclohexyl dicarboxylic acid, adipic acid, Azelaic Acid, decanedioic acid, 1,3-propanedicarboxylic acid, tetrachlorophthalic acid, maleic acid, Fumaric acid, itaconic acid, malonic acid, suberic acid, succinic acid, 2-methylsuccinic acid, 3,3-diethyl glutarate, 2,2-dimethyl amber Amber acid, dodecanedioic acid, endo-methylene group tetrahydrophthalic acid, dimer fatty acid, trimer fatty acid, citric acid or inclined benzene Three acid.Corresponding anhydride can also be used as acid source.

If average functionality >=2 of polyhydric alcohol to be esterified, it is also possible to use monocarboxylic acid, such as benzoic acid and hexane first Acid.

The example of the hydroxy carboxylic acid that can function together as reactant in the preparation containing the PEPA of terminal hydroxy group includes Hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxy stearic acid etc..Suitably lactone especially includes caprolactone, butyrolactone and homology Thing.

The polycarbonate polyol that can use is the Merlon of hydroxyl, such as PCDL.They can lead to Percarbonic acid derivant, such as diphenyl carbonate, dimethyl carbonate or phosgene and polyhydric alcohol, the reaction of preferred diol obtains, maybe can lead to Peroxidating alkene such as expoxy propane and CO₂Copolyreaction obtain.

The example of this kind of glycol include ethylene glycol, 1,2-and 1,3-propylene glycol, 1,3-and 1,4-butanediol, 1,6-oneself two Alcohol, 1,8-ethohexadiol, neopentyl glycol, 1,4-hydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, 2,2,4-trimethyl amyl-1, 3-glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol, polytetramethylene glycol, bisphenol-A and the glycol of lactone-modified the above-mentioned type.

Replace or in addition to pure PCDL, it is possible to use polyether polycarbonate glycol.

The polyester ether polylol that can use is containing ether group, ester group and the compound of OH group.Have most 12 The organic dicarboxylic acid of individual carbon atom is applicable to prepare described polyester ether polylol, and be preferably used alone or as a mixture has >=4 Aliphatic dicarboxylic acid or aromatic dicarboxylic acid to≤6 carbon atoms.Example includes suberic acid, Azelaic Acid, decane dicarboxylic, Malaysia Acid, malonic acid, phthalic acid, 1,5-pentanedicarboxylic acid. and decanedioic acid, especially 1,3-propanedicarboxylic acid, fumaric acid, succinic acid, adipic acid, adjacent benzene two Formic acid, p-phthalic acid and M-phthalic acid.The derivant of these available acid includes such as their anhydride and they and tool There are >=ester of the low-molecular-weight monofunctional alcohol of 1 to≤4 carbon atom and half ester.

It is many that the polyether polyol obtained by the alkoxylate of starter molecules such as polyhydric alcohol is used as the described polyether ester of preparation The other component of unit's alcohol.This starter molecules is the most dual functional, but can also higher optionally with certain content Sense, the particularly starter molecules of trifunctional.

Starter molecules includes such as having preferably >=18g/mol to≤400g/mol or >=62g/mol to≤200g/ The glycol of number-average molecular weight Mn of mol, as 1，2-ethandiol, 1,3-PD, 1,2-PD, BDO, 1,5-penta Enediol, 1,5-pentanediol, neopentyl glycol, 1,6-HD, 1,7-heptandiol, 1,8-ethohexadiol, 1,10-decanediol, 2-first Base-1,3-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 2-butyl-2-ethyl-1,3-the third two Alcohol, 2-butylene-Isosorbide-5-Nitrae-glycol and 2-butyne-Isosorbide-5-Nitrae-glycol, ether glycol, such as diethylene glycol, triethylene glycol, TEG, two fourths Glycol, three butanediols, four butanediols, two hexanediol, three hexanediol, four hexanediol, and alkylene glycol such as diethylene glycol is oligomeric Mixture.

In addition to glycol, it is also possible to number-average used along > 2 to≤8 or the polyhydric alcohol of >=3 to≤4, such as 1,1,1- Trimethylolpropane, triethanolamine, glycerol, sorbitan and tetramethylolmethane and have mean molecule quantity be preferably >=62 The polyethylene glycol oxide initial by triol or tetrol of g/mol to≤400g/mol or >=92 g/mol to≤200g/mol is polynary Alcohol.

Polyester ether polylol also can the alkoxylate of product by being obtained by the reaction of organic dicarboxylic acid Yu glycol Prepare.The derivant of these acid that can use includes such as their anhydride, such as phthalic anhydride.

Polyacrylate polyol can pass through the radical polymerization of the ethylenically unsaturated monomers of hydroxyl or pass through hydroxyl Ethylenically unsaturated monomers optionally and the free-radical polymerized incompatible acquisition of other ethylenically unsaturated monomers.The example includes acrylic acid Ethyl ester, butyl acrylate, 2-EHA, isobornyl acrylate, methyl methacrylate, methacrylic acid second Ester, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, styrene, acrylic acid, acrylonitrile and/ Or methacrylonitrile.The suitably ethylenically unsaturated monomers particularly acrylic acid 2-hydroxy methacrylate of hydroxyl, methacrylic acid 2- Hydroxy methacrylate, can by expoxy propane add on acrylic acid obtain Hydroxypropyl acrylate isomer mixture and ring can be passed through Ethylene Oxide adds to the Hydroxypropyl methacrylate isomer mixture obtained on methacrylic acid.Terminal hydroxy group can also be for be protected The form protected.Suitably radical initiator is selected from azo-compound, such as azo isobutyronitrile (AIBN), or selected from peroxide Such as di-t-butyl peroxide.

In another embodiment, described isocyanate-reactive component A) comprise have >=200 mg KOH/g extremely The short-chain polyol of the polyester ether polylol of the hydroxyl value of≤600 mg KOH/g and having >=800 mg KOH/g hydroxyl values.Close Suitable polyester ether polylol especially difunctionality polyester ether polylol, it passes through oxyalkylene especially ethyleneoxide addition to adjacent benzene Obtain on the mixture of dicarboxylic acid anhydride, diethylene glycol and ethylenediamine and there are >=275 mg KOH/g to≤325 mg KOH/g OH value.This series products can be obtained with trade name Desmophen VP.PU 1431 by Bayer MaterialScience AG. Described PEPA can also have >=the OH value of 290 mg KOH/g to≤320 mg KOH/g.Short-chain polyol is special It is that there is >=the polyhydric alcohol of 2 to≤6 carbon atoms.Glycerol is preferred.This compound has the OH value of 1827 mg KOH/g. Add short-chain polyol and allow to advantageously increase the polarity of polynary alcohol phase.

In one embodiment, component A) completely or partially by comprise equally hydrophobic parts and hydrophilic parts and There is the isocyanate-reactive compound A2 of the average hydroxy functionality more than 1) constitute.These compounds A2) can carry equally For surfactant function.Compound A2) hydrophobic parts comprise there is the saturated of at least 6 carbon atoms or undersaturated hydrocarbon Chain, and wherein said hydrophilic parts comprises oxyalkylene units and/or ester units.Compound A2) example be described in WO In 2012/146568.

Compound B2) example include the alkanol of alkoxylate, the alkyl phenol of alkoxylate, the fatty acid of alkoxylate, The fatty acid ester being esterified with glycol or triol.

Compound A2) there is 4-18, preferably 8-16 and the HLB value of particularly preferred 10-15.Described hydrophobic parts comprises tool There are at least 6 carbon atoms, preferably at least 8 carbon atoms, preferably at least 12 carbon atoms and particularly preferably at least 14 carbon atoms Saturated or undersaturated hydrocarbon chain.

Isocyanate-reactive compound A2) saturated hydrocarbon chain such as can be by being esterified of polyhydric alcohol satisfied fatty acid Arrive.Suitably an example of satisfied fatty acid is 2 ethyl hexanoic acid.Certainly, undersaturated hydrocarbon chain is except (H) C=C (H) shape Saturation unit CH2 can also be contained outside the unit of formula.This can be by realizing with unsaturated fatty acid ester.Suitably One example of unsaturated fatty acid is oleic acid ((Z)-9-octadecenoic acid).Can also use by natural oil such as soybean oil or dish The mixture of the fatty acid that seed oil obtains.

Described isocyanate-reactive compound A2) it is preferably the compound of liquid at 20 DEG C, it preferably has less than 15 000 mPas, the viscosity of more preferably less than 5000 mPas.Viscosity can such as measure according to DIN 53019.

Isocyanate-reactive compound A2) hydrophilic region preferably comprise ethylene oxide unit [CH2 CH2 O] And/or carboxylic ester units.Compound A2) can such as be obtained by the part alkoxylate of the polyhydric alcohol of at least trifunctional, with The OH group making described polyhydric alcohol can be used for the esterification of fatty acid.Compound A2) additionally can such as by oleic acid with oneself two The esterification of acid, trimethylolpropane and/or diethylene glycol obtains.Isocyanate-reactive compound A2) preferably per molecule has Average OH group number be 1.5-5, particularly preferably 1.8-3.5 and 2.5-3.5.

In another embodiment, isocyanate-reactive compound A2) there are >=50 mg KOH/g to≤500 The hydroxyl value of mg KOH/g.This value can determine according to DIN 53240.The preferred scope of OH value be >=70 mg KOH/g to≤ 400 mg KOH/g and particularly preferably 50 mg KOH/g to≤100 mg KOH/g and >=100 mg KOH/g to≤300 mg KOH/g.In the case of mixture, this refers to average OH value.

These embodiments can arbitrarily be mutually combined.Particularly preferably there are >=50 mg KOH/g to≤100 mg The hydroxyl value of KOH/g and the isocyanate-reactive compound A2 that average OH group number is 1.8-3.5 of per molecule).

In another embodiment, described isocyanate-reactive compound A2) content based on this mixture total Weight is calculated as >=0.5 weight % to≤40 weight %.Described content is preferably >=2 weight % to≤30 weight % and more preferably >=5 weight % to≤20 weight %.

In another embodiment, described isocyanate-reactive compound A2) hydrophilic parts comprise beginning ester Change the fatty acid of (eingeestert), and content gross weight based on the described mixture meter of the described fatty acid starting esterification For >=0.5 weight % to≤25 weight %.Preferably content is >=2 weight % to≤15 weight %, particularly preferably >=4 weights Amount % is to≤10 weight %.

In another embodiment, described isocyanate-reactive compound A2) by the polyhydric alcohol of part alkoxylate Reaction with fatty acid can obtain.

The most described isocyanate-reactive compound A2) comprise the carboxylic acid of the sorbitan of alkoxylate Ester.

Further preferably, described isocyanate-reactive compound A2) be the ester leading to formula (I):

(I)

Wherein w+x+y+z >=16 are to have >=the saturated or undersaturated hydrocarbon of 12 to≤18 carbon atoms to≤22 and R Base.

One particularly preferred example is the polysorbate80 that formula (II) describes:

(II)

Wherein w+x+y+z=20.

The most described mixture additionally comprises other surface active agent composition E).

Suitably surfactant E) selection start to be not restricted by.Advantageously, described surfactant allows foaming Agent is at isocyanate-reactive middle formation emulsion or microemulsion mutually.Specially suitable surfactant includes such as alkoxylate Alkanol such as has >=the linear or branched alkanol of 6 to≤30 carbon atoms with there are >=5 to≤100 oxyalkylene lists The ether of ployalkylene glycol of unit, the alkyl phenol of alkoxylate, the fatty acid of alkoxylate, the sorbitan of alkoxylate Carboxylate (especially polysorbate80), fatty acid ester, polyalkylene amine, alkyl sodium sulfate ester, phosphatidylinositols, the table of fluorination Face activating agent, comprise surfactant such as polysiloxane-polyoxyalkylene copolymer and/or the 2-Sulfosuccinic acid of polysiloxane group Double (2-ethyl-1-hexyl) ester.The example of such surfactant include alkyl sodium sulfate ester or 2-Sulfosuccinic acid double (2-ethyl- 1-hexyl) ester.Described surface active agent composition E) it is preferably the compound of liquid at 20 DEG C, it preferably has less than 15 000 MPas, the viscosity of more preferably less than 5000 mPas.Viscosity can such as measure according to DIN 53019.

Described surface active agent composition E) number-average molecular weight Mn for example, >=100 g/mol that can have to≤8000 G/mol, preferably >=200 g/mol are to≤5000 g/mol and more preferably >=500 g/mol to≤2500 g/mol.

In one embodiment, described surface active agent composition E) hydrophobic parts comprise that to have at least 4 carbon former Son, preferably at least 6 carbon atoms, preferably at least 12 carbon atoms and particularly preferably at least 14 carbon atoms saturated or unsaturated Hydrocarbon chain.Surface active agent composition B) saturated or undersaturated hydrocarbon chain can such as pass through fatty acid alcohol (Fett Urealkohol) or fatty acid oxirane or expoxy propane alkoxylate prepare.

The preparation of polyurethane foam uses supercritical or near-critical foaming agent B).In the present invention, following when meeting During condition, there is near-critical condition: (T_cT)/T≤0.4 and/or (p_c− p)/p ≤ 0.4.Here, T is the method In leading temperature, T_cBeing the critical temperature of foaming agent or blowing agent blends, p is pressure leading in the method and p_cIt is to send out Infusion or the critical pressure of blowing agent blends.When following situation, preferably there is near-critical condition: (T_c–T)/T≤ 0.3 And/or (p_c-p)/p≤0.3, particularly preferably (T_cT)/T≤0.2 and/or (p_c-p)/p≤ 0.2.Without being bound by theory And think, by selecting suitable surface active agent composition, form supercritical comprising the middle mutually of isocyanate-reactive component Or the emulsion of near-critical foaming agent or microemulsion.

Described foaming agent preferably can form the phase of oneself in the reactive mixture.Such as can use supercritical titanium dioxide Carbon.Carbon dioxide can be formed in the course of reaction forming polyurethane foam, such as by isocyanates and water or anti-with acid Should.The example of other foaming agent is linear C₁-C₆-hydrocarbon, branched C₄-C₆-hydrocarbon and ring-type C₃-C₆-hydrocarbon.The particular example of foaming agent There are methane, ethane, propane, normal butane, iso-butane, pentane, isopentane, Pentamethylene., isohexane and/or hexamethylene.Additionally Example has methane, ethane, propane, normal butane, iso-butane, pentane, isopentane, Pentamethylene., hexane, isohexane, 2,3-diformazan Base butane and/or the part of hexamethylene or fluoridized derivant.Carbon dioxide or the carbon dioxide content that have are preferably used More than 30 weight %, preferably greater than 50 weight % and the blowing agent blends of more preferably greater than 70 weight %.

Described foaming agent content in the reactant mixture comprising whole isocyanate-reactive component is based on described different Polyisocyanate reactant component meter can be such as >=5 weight % to≤60 weight %.Described foaming agent is comprising component A), B), C), D), E) and reactant mixture F) in content can be such as >=3 weight % to≤60 weight %, preferably >=4 weight % To≤40 weight % and particularly preferably >=5 weight % extremely≤30 weight %.

Component C) it is polyisocyanates, i.e. there is >=the isocyanates of the NCO degree of functionality of 2.The reaction that accordingly, there exist mixes Compound can react and obtain polyurethane, polyureas or polyisocyanurate foam.

This reactant mixture can such as directly produce in mixing head.

The example of this type of suitable polyisocyanates includes 1,4-fourth diisocyanate, 1,5-penta diisocyanate, 1,6- Hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4-and/or 2,4,4-trimethyl-six are sub- Double (4,4'-isocyanatocyclohexyl) methane of methyl diisocyanate, isomery or its there is the mixing of any content of isomer Thing, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-and/or 2,6-toluene di-isocyanate(TDI) (TDI), 1,5- Naphthalene diisocyanate, 2,2'-and/or 2,4'-and/or 4,4'-methyl diphenylene diisocyanate (MDI) and/or higher level are same It is thing (polymeric MDI), double (2-isocyanato-acrylate-2-the yl)-benzene (TMXDI) of 1,3-and/or l, 4-, the double (isocyano of l, 3- Close methyl) benzene (XDI) and containing 2,6-bis-isocyanato-caproic acid Arrcostab (lysine two Carbimide. of C1 to C6 alkyl Ester).It is preferred from the isocyanates of methyl diphenylene diisocyanate series in the case.

In addition to above-mentioned polyisocyanates, it is also possible to certain content used along there is urea diketone, isocyanuric acid ester, amino Formic acid esters, carbodiimide, uretonimine, allophanate, biuret, amide, imido are for oxadiazinediones and/or diazine three The unmodified polyisocyanates such as 4-that the modifying diisocyanates of ketone structure and per molecule contain more than two NCO group is different Cyanate radical closes methyl isophthalic acid, 8-octane diisocyanate (nonane triisocyanate) or triphenyl methane-4,4', 4 "-three Carbimide .s Ester.

Described isocyanates can be by having >=isocyanates of the NCO degree of functionality of 2 with there are >=62 g/mol The available prepolymer of reaction of the polyhydric alcohol of the molecular weight of extremely≤8000 g/mol and the OH degree of functionality of >=1.5 to≤6.

Certainly other conven-tional adjuvants and additive F can also be used) such as catalyst, fire retardant, releasing agent, filler etc. To prepare polyurethane foam.

Described component A), B), C), D) and optional E) and optional F) preferably exist with following amount:

A) 0-60 weight %, particularly 10-60 weight %, preferably 15-50 weight %

B) 2-40 weight %, preferably 4-15 weight %

C+D) content sum is 20-70 weight %, preferably 30-60 weight %, wherein C): the ratio of weight percent D) is 0: 100-90:10, preferably 1:99-75:25.

E) 0-20 weight %, preferably 1-20 weight %, particularly preferred 1-15 weight %

F) 0-10 weight %, preferably 0.001-10 weight %.

Weight percent (" weight % ") compositions meter based on whole reactant mixture in each case, unless additionally Explanation.In whole compositions, whole percentage rate sums are 100 weight %.

In the case of the content of component A is not 0, described polyisocyanate component C) and amphipathic isocyanates D) in NCO group number and component A) isocyanate-reactive group number relative to each other can for example, >=50:100 to≤500: The quantity ratio of 100.This parameter can also be >=160:100 to≤330:100 or >=80:100 to≤140:100.

According to the present invention, by foaming agent B) with amphipathic isocyanates D) mix, wherein make foaming agent be in supercritical or Near-critical state.Component B) component C can also be previously positioned at) and mixture D) in.

By component B) completely or partially at amphipathic isocyanates D) or at isocyanate component C) and mixture D) Middle emulsifying.A part component B) component A2 can also comprised) and NCO reactive compounds A) in emulsifying.

Comprise component A), B), C), D) and optional E) and optional F) polyurethane system may then pass through component A) with optionally except isocyanate component C) and D) in addition to other component and amphipathic isocyanates and polyisocyanates such as High-pressure mixing head is mixed to get, amphipathic isocyanates D described at least a part of which) or described amphipathic isocyanates and polyisocyanate Cyanate C) mixture contain foaming agent, it is supercritical or near-critical state and mixing that this foaming agent is in for foaming agent Condition in Tou is supercritical or near-critical for foaming agent.

In one embodiment, component A) (it optionally contains other component) equally contain supercritical or closely face The foaming agent of boundary's state.When component A) containing providing the NCO reactive compounds A2 of surfactant function) time or work as It is additionally present component E) time, this is possible.

Can be such as >=40 bar to≤300 bar for preparing the convenient pressure of described polyurethane foam.Properly Temperature for example, >=10 DEG C to≤110 DEG C, preferably >=25 DEG C to≤80 DEG C.Particularly preferably CO₂Pressure more than critical point And temperature, i.e. >=73.7 bar and >=31 DEG C.

In another embodiment, described polyisocyanate component C) comprise the diphenyl methane of monomer and/or polymerization- 4,4'-diisocyanate.This type of polyisocyanates such as by Bayer MaterialScience as diphenyl methane-4,4'- The mixture of the homologue of diisocyanate (MDI) and isomer and higher functional can with trade name Desmodur 44V70L ?.

In another embodiment, described polyurethane foam has >=20 kg/m³To≤160 kg/m³Apparent close Degree.Apparent density can measure according to DIN EN 1602 and be preferably >=30 kg/m³To≤120 kg/m³More preferably >= 30 kg/m³To≤80 kg/m³.For the foam of the present invention, preferably application is adiabatic, be such as used for manufacturing insulation board, Composite metal plate or adiabatic for refrigerator.

The method that the invention further provides for prepare polyurethane foam, it comprises the steps:

-component A will be comprised), B), C), D) and optional E) and optional F) mixture introduce in the mould of Guan Bi, Qi Zhongshe Put described Guan Bi mould so that its internal volume and/or its internal leading pressure can be by outside shadows after introducing mixture Ring and change.

-make to comprise component A), B), C), D) and optional E) and optional F) mixture stop in described Guan Bi mould >= The scheduled time of 0 second；With

-increase the internal volume of described Guan Bi mould by external action and/or reduce the pressure that described Guan Bi mould inside is leading Power.

One embodiment of the method for the present invention is made up of following steps:

-at an elevated pressure, compound A is such as provided in mixing head), B), C), D) and optional E) and optional F) Mixture；With

-from mixing head, such as discharge described mixture, wherein leading in the mixture in discharge process pressure drop is as little as Atmospheric pressure.

During discharging described mixture from mixing head, pressure drop as little as atmospheric pressure leading in the mixture. Atmospheric pressure should be understood to particularly relate to >=the pressure of 0.9 bar to≤1.1 bar herein.Foaming agent is changed into Asia by this Critical state and be preferably changed into gaseous state.Such as, reactant mixture can be incorporated into open mold from mixing head simply or Person can be used continuously to manufacture sheet material, such as, carried out by free foaming equipment or Dual-conveying tall equipment.Understand according to the present invention Ground includes, leaves mixing head and release of pressure at described reactant mixture and also sets up intermediate station between atmospheric pressure, wherein leading pressure Power is between the pressure in mixing head and atmospheric pressure.

In an embodiment of the method for the present invention, providing compound A), B), C), D) and optional E) and times The F of choosing) mixture after, the pressure of >=40 bar to the pressure of≤200 bar, preferably >=60 bar to≤150 bar Power, the pressure of particularly preferably >=70 bar to≤120 bar accounts for leading.In mixing head, the downstream with mixing head can be deposited especially In this state.Described pressure can also be >=80 bar to≤120 bar.Under this type of pressure, can keep for used Infusion supercritical or near-critical condition.

In another embodiment of the method for the present invention, in mixing head or at the settling means downstream of mixing head, With improve discharge comprise component A), B), C) and D) and optional E and optional F) mixture during flow resistance.This type of The example of device can include orifice plate, grid, gap grid and/or sieve, and from flow direction, it is arranged on mixing head mixing The downstream of room.The raising of flow resistance can affect the pressure that reactant mixture was had before discharging from mixing head targetedly Power.The pressure so set can be less than the pressure in the component mixed process of reactant mixture.This allows to impact foaming Agent microdroplet or the formation of foaming agent vesicle and expansion.Such device is such as described in WO 2001/98389 A1.

Embodiment as described above is intended to describe the present invention, the invention is not limited in this.Described embodiment is permissible Combination in any, unless contrary by context is evident as.

Vocabulary:

Desmodur PU 1806: diphenyl methane-2,4'-diisocyanate and diphenyl methane-4,4'-diisocyanate (MDI) mixture, Bayer MaterialScience AG

Isophthaloyl chloride, CAS 99-63-8, Fluka can obtain

Methoxy poly (ethylene glycol) 350, CAS 9004-74-4, Fluka can obtain

Ethyl hexanol, CAS 104-76-7, Fluka can obtain.

The preparation of amphipathic polyisocyanates

Embodiment 1

It is pre-placed the Desmodur PU1806 of 412.5 g and 1.1 g isophthaloyl chlorides and is heated to 40 DEG C.At 20 minutes The most under agitation drip 137.5 g methoxy poly (ethylene glycol)s 350.Then temperature is increased to 80 DEG C and stirs 2 hours further. Obtain the 551.2 amphipathic polyisocyanates of g (NCO content 22.05 %).

Embodiment 2

It is pre-placed the Desmodur PU1806 of 355.6 g and 1.1 g isophthaloyl chlorides and is heated to 40 DEG C.At 20 minutes The most under agitation drip 192.5 g methoxy poly (ethylene glycol)s 350.Then temperature is increased to 80 DEG C and stirs 2 hours further. Obtain the 552.10 amphipathic polyisocyanates of g (NCO content 17.18 %).

Embodiment 3

It is pre-placed the Desmodur PU1806 of 223.95 g and 1.19 g isophthaloyl chlorides and is heated to 40 DEG C.At 20 points 74.85 g ethyl hexanols are under agitation dripped in clock.Then temperature is increased to 80 DEG C and stirs 2 hours further.Obtain 300 The amphipathic polyisocyanates of g (NCO content 16.74 %).

Embodiment 4:

By amphipathic isocyanates and the CO of 10 weight % of embodiment 1₂(based on described amphipathic isocyanates meter) at 50 DEG C and Mix under p=130 bar.This provides a kind of mixture, and it appears as single-phase with eyes, but the light being made by laser beam dissipates Penetrating susceptible of proof is that microemulsion (causes scattering of light by the structure of mixture, and laser beam is visible in this phase, sees figure 1)。

Embodiment 5 and 6:

The amphipathic isocyanates using embodiment 2 and 3 repeats embodiment 4, obtains identical result in each case and (sees Fig. 1).

Claims

1. polyurethane, poly-isocyanurate or polyurea foam, it can obtain by the reaction of the mixture comprising following component:

A) optional isocyanate-reactive compound (" NCO reactive compounds ")；

B) foaming agent, it is selected from linear, branched or ring-type C1-C6 hydrocarbon, linear, branched or ring-type C1-C6 hydrofluorocarbons, N₂、 O₂, argon and/or CO₂, wherein said foaming agent B) and it is in supercritical or near critical state；

C) optional polyisocyanates；

D) amphipathic isocyanates；With

E) optional surfactant；With

F) other optional auxiliary agent and additive.

2. polyurethane as claimed in claim 1 or 2, poly-isocyanurate or polyurea foam, wherein said amphipathic Carbimide. Ester has the HLB value of 1-18.

3. polyurethane as claimed in claim 1 or 2, poly-isocyanurate or polyurea foam, wherein said amphipathic Carbimide. Ester has the HLB value of 2-17.

4. polyurethane as claimed in claim 1 or 2, poly-isocyanurate or polyurea foam, wherein said amphipathic Carbimide. Ester has the HLB value of 3-16.

5. polyurethane, poly-isocyanurate or the polyurea foam as according to any one of claim 1-4, wherein said amphipathic The content of isocyanates is calculated as 5-70 weight % based on whole composition weight.

6. polyurethane, poly-isocyanurate or the polyurea foam as according to any one of claim 1-5, wherein said amphipathic The hydrophobic parts of isocyanates is to be selected to comprise to have the unitary of the saturated of at least 4 carbon atoms or aliphatic unsaturated hydrocarbon or polynary The group of the alcohol of alcohol.

7. polyurethane, poly-isocyanurate or the polyurea foam as according to any one of claim 1-5, wherein said amphipathic The hydrophilic parts of isocyanates is selected from simple function or the group of the alcohol of multifunctional polyoxyalkylene.

8. polyurethane, poly-isocyanurate or the polyurea foam as according to any one of claim 1-7, wherein said A)-F) Whole compositions exists with following weight percent (weight %):

A) 0-60 weight %, preferably 10-60 weight %

B) 2-40 weight %,

C+D) 20-70 weight %, wherein C): the ratio of weight percent D) is 0:100-75:25, preferably 1:99-75:25,

E) 0-20 weight %,

F) 0-10 weight %,

Wherein all content sum is 100 weight %.

9. polyurethane, poly-isocyanurate or the polyurea foam as according to any one of claim 1-8, wherein component A) only or Part is containing component A2), component A2) comprise hydrophobic parts and hydrophilic parts and there is the average hydroxy functionality more than 1,

Wherein said hydrophobic parts comprises and has the saturated of at least 6 carbon atoms or aliphatic unsaturated hydrocarbon, and

Wherein said hydrophilic parts comprises oxyalkylene units and/or ester units.

10. polyurethane as claimed in any one of claims 1-9 wherein, poly-isocyanurate or polyurea foam, wherein said polyisocyanate Isocyanate component C) comprise the diphenyl methane-4,4'-diisocyanate of monomer and/or polymerization.

11. polyurethane, poly-isocyanurate or the polyurea foam as according to any one of claim 1-10, it has >=20 kg/m³To≤160 kg/m³Apparent density.

12. for preparing the side of polyurethane, poly-isocyanurate or polyurea foam as according to any one of claim 1-11 Method, it comprises the steps:

-component A will be comprised), B), C), D) and optional E) and optional F) mixture introduce in Guan Bi mould, Qi Zhongshe Put described Guan Bi mould so that its internal volume and/or its internal leading pressure can pass through after introducing described mixture External action changes；

13. for preparing the side of polyurethane, poly-isocyanurate or polyurea foam as according to any one of claim 1-11 Method, it comprises the steps:

-at an elevated pressure provide as one or more in claim 1-10 described in compound A), B), C), D) and times The E of choosing) and optional F) mixture；With

-discharge described mixture, wherein leading in the mixture in discharge process pressure drop as little as atmospheric pressure.

14. methods as described in claim 12 or 13, wherein by component B) be previously positioned at whole or in part amphipathic different Cyanate D) in or at isocyanate component C) and mixture D) in.

15. methods as claimed in claim 14, wherein by a part component B) be previously positioned at comprise component A2) NCO Reactive compounds A) in.